Hydroxy-pyridone-monosulfonic acids

ABSTRACT

4-SUBSTITUTED-6-HYDROXY-2-PYRIDONE-5-SULFONIC ACIDS WHICH MAY BE OPTIONALLY SUBSTITUTED IN THE 1- AND 3-POSITIONS, PREPARATION THEREOF FROM THE CORRESPONDING 6-HYDROXY-2-PYRIDONE DERIVATIVES BY SULFONATION AND UTILITY THEREOF IN THE PREPARATION OF DYESTUFFS.

United States Patent Heinrich et al.

[451 Oct. 14, 1975 HYDROXY-PYRIDONE-MONOSULFONIC ACIDS [75] lnventors: Ernst Heinrich, Frankfurt am Main-Fechenheim; Rolf Muller, Frankfurt am Main, both of Germany [73] Assignee: Cassella Farbwerke Mainkur AG,

Germany [22] Filed: Oct. 21, 1974 [21] Appl. No.: 516,768

Related US. Application Data [62] Division of Ser. NO. 241,845, April 6, 1972, Pat. NO.

[30] Foreign Application Priority Data Apr. 10, 1971 Germany 2117753 52 u.s.c| ..260/21811;260/156;260/247.1;

260/247.2 A; 260/289 R; 260/294.9; 260/295.5 A; 8/41 A; 8/41 E Primary Examiner--Alan I... Rotman Attorney, Agent, or Firm-Connolly and Hutz [57] ABSTRACT 4-substituted-6-hydroxy-2-pyridone-5-sulfonic acids which may be optionally substituted in the land 3- positions, preparation thereof from the corresponding 6-hydroxy-2-pyrid0ne derivatives by sulfonation and utility thereof in the preparation of dyestuffs.

5 Claims, No Drawings 1 7. t HYDROXY-PYRIDONE-MONOSULFONIC. ACIDS CROS -REFER NC TO REL TED/AP LICATION This application is a division of application ser. No. 241,845, filed Apr. 6,. 1972, now US. .Pat. No. 3.867.392.

The .present invention relates to hydroxy-pyridonemonosulfonic acids of the formula I I tuted cyclohexyl wherein said cyclohexy l substituent is 25 selected from the group consisting of chloro, methyl and methoxy; Y is hydrogen; cyano; alkyl having 1 to 6 carbon atoms; substituted alkyl wherein the alkyl moiety has from 1 to 6 carbon atoms and said substitu ent is selected from the group consisting of cyano, hydroxy, methoxy, amino, me thylamin o anddimethylamino; cyclohexyl; substituted cyolohexy] wherein said substituent is selected from the group consisting of chloro, methyl and methoxy; -COR wherein R is amino, methylamino, dimethylamino, cyanoethyl, methoxymethyl, cyclohexyl, cyclohexylamino, alkyl having l to 2 carbon'atoms,

cH N l or morpholino or -SO R wherein R is methyl, cyclohexyl or chlorocyclohexyl; or X and Y together consi- CH CH H; CH1

Ho s I H'O' S I CN H035 I Ho s I u u u n HO 0 Ho 0 Ho Ho 1 o H H CH3 tute a (CH,).,-- group; and Z is hydrogen; alkyl having 1 to 6 carbon atoms; substituted alkyl wherein the alkylmoiety has from 1 to 6 carbon atoms and said substituent is selected from the group consisting of cyano, hydroxy, methoxy, amino, methylamino, dimethylamino and Y CH --N CH2 cyclohexyl; substituted cyclohexyl wherein the substituent is selected from the group consisting of chloro, methyl and methoxy; amino; monoalkylamino having 1 to 4 carbon atoms or dialkylamino having 1 to 4 carbon I atoms in each alkyl moiety.

The preferred compounds of the present invention are of formula I wherein: X is alkyl having I to 4 carbon atoms,

Y is hydrogen or cyano and i x p Z is hydrogen, amino, alkyl having 1 to 4 carbon atoms, aminoalkyl having 1 to 4 carbon atoms methylaminoalkyl wherein said alkyl has 1 to 4 carbon atoms or monoalkylamino having 1 to 4 carbon atoms. When X and Z'are alkyL'they preferably have from 1 to 2'carbon atoms. g V The following formulae represent the particularly preferred compounds.

Those skilled in the art will appreciate the fact that the hydroxy-pyridone-monosulfonic acids of formula I of the present invention may assume a variety of tauto 45 meric forms such' as illustrated by the following:

/ Y H0 5 Y H0 5 H n N u OH O O O O z z I 2 la lb lc Moreover and if Z is hydrogen, a variety of tautomeric forms may exist as represented by the following:

- 3 4 It is expresslyunderstood, that formula I in both the scribed in Tthe mono gra pli -of 'E. k liri g sber gi P yridine specification and claims of the present invention, emand its Derivatives, Part. 3" (Interscience Publishers braces within its scope the tautomers thereof such a i962) published in the Series ofiMonograph's-The represented. by, the foregoing formulae. Chemistry of Heterocyclic Compounds, edited by A. The compounds of the present invention may be pre- 5 Weissgerber. ,or by condensation, in, an alkaline mepared, for example, by treating the appropriate 6- dium, of sulfo acetamides or acetates with correspondhydroxy-2-pyridone of the formula: ingly substituted B-ketocarboxylic acid esters ,,or B-ketocarbonamides. I The preparation of the fl-ketocarboxylic acidesters -10 of the general formula VIII can also be done according to methods knwon per se, for example by acylation of sodium aceto acetate with an acid chloride of the general formula IX:

x co c1 IX or by acylation of ethyl aceto acetate (formula X) with an acid chloride of the general formula IX in the presh r i X, Y d Z h h b i meanings, ence of magnesium according to the method of M. Viswith sulfonating agents, preferably with chlorosulfonic Contini and Merckling; desc'lrbed in e a acid or oleum. Chimica Acta XXXV, (19522280-2282 whereby the The initial coinpound of the general formula VI may compound of the general formula XI is formed which also, be present in various tautomeric forms. The initial is converted into theB-ketooarboxylic acid ester'of'the compounds may .be prepared analogously to the methgeneral formula VIII a by subsequent acid cleavage; for 0d described by Guareschi, in Berichte der Deutschen example with sodium methylate in methanol according Chemischen Gesellschaft Referate-29,,Vol. 4-( I897), to the method of H. :Hundsdiecke'r described in Bepages 654-656, i.e. by condensationv of correspondrichte der deutschen cliemische'n Gesellschaft" 75 ingly substituted acetamides or acetic acid hydrazides -(-l942),,4,54

H x c=o CH,C-CH;, ClCOX m /CH-COCH, b) n c ooc H,c,ooc

x IX XI x-c=o I I x c=o CH 0Na c) CH,

' /CHC0CH3 H5C2OOC HQCOOC i .X! i Villa of the general formula VII withcorrespondingly,substi- Cyanoacetamides of 'fthe generalformuli; VIIa tuted B -ke-tocarboXylic acid esters of the general for- NCCH 'CO=NHZ I vna mula VIII in accordance with the following reaction may be prepared according to the process of Naik and equation: Bhat, described in Quarterly Journ. Ind. Chem. Sec."-

4, 547-551(1927). v If a cyanoacetamide of the general formula VIIa is T cbndensed, zfor instance, with a ketocarboxylic acid C X ester of the general formula VIIIa, a compound of the 1 general formula VI is obtained according to the above- H,CY O Y given reaction scheme (a), in which Y is equal to CN C C=O i and which is represented by the following general for- N mula Vla HO 0 0 0R HN X I g i Z d) I VI V" VI HZ 1$O 1H =(|3 N' H o c c t CH;IOH H0 o ocH X, Y. and Zhave the before mentioned meanmgs,-R stands for an alcyl group, inparticular, the ,methyl or Z Z ethyl group. They may also'be prepared according to other methods, for instance, according to that de- VIlla Vlla Vla are obtained.

The condensation can be effected according to the process of M. Bobbitt and D. Scola described in Journ. Org. Chem. 25 (1960) 560-560 (example 1).

Compounds of the general formula Vla may also be used for the preparation of compounds of the general formula VI, wherein Y is different from CN. By way of example, according to the method of Gibson and Simonsen described in Journ. Chem. Soc." 1929, 10744030, it is possible to split off the 3-positioned CN-group from compounds of the general formula Vla 10 Scola, loc. cit. and with subsequent cleavage of the by heating up to 120C. in sulfuric acid of 60% whereby compounds of the general formula VI!) C=O H2C-CN Y 1 i i -H2O e) Y-CH C=O -R-OH l-IO 0=c HN 0R I, Z '7 VIllb lla xn H0 0 HO 0 Xll 'vld X The required a-alkyl or cyclohexyl -B-ketocarboxylic acid esters are easy to prepare analogously according to the direction for the reparation of the eth l-nl I Y N butylacetoacetate as described in Organic Synthesis, I O Coll. Vol. I, 248.

Z Starting materials of the general formula K bonamide group according to German document No.

2,045,851 laid open to public inspection and compounds of the general formula V10 Vlc HO Compounds of the general formula VI,v in which Y cyano group in 3-position in accordance with the method by Gibson and Simonsen loc. cit. under the following reaction scheme:

can be prepared by condensing compounds of the general formula V1!) with compounds of the general formulae XIII and XIV in glacial acetic acid using zinc chloride as condensation agent at temperatures of about to C. according the following reaction equations:

ZnCh/ 1 4051 so'ic If in the above-given reaction equation (e) the cyclo-hexanone-Z-carboxylic ethyl ester (prepared according to Organic Synthesis, Coll. Vol. II, 532) is employed as B-keto-ester component, the initial compound of the general formula VI is obtained according to the reaction equations (2) and (I), wherein X and Y constitute together a- --(CH ),g roup.'

The compounds of the present invention are valuable intermediates, in particular for the preparation of dye stuffs, preferably of azo dyestuffs. In the production of 5 azo dyes the compounds of the present invention are utilized as coupling components. The azo dyes are pre pared in a manner known per se by diazotation and coupling. A diazo component is diazotized and 'the diazo solution is admixed with an aqueous solution that contains the sodium salt of a compound of the present Initial compounds of the generalformula VI, wherein Y stands for a COR-group, in which R may be amino, methylamino, diethylamino, cyclohe'xyl amino morpholino or or can also be prepared analogously in accordance with the method by U. Basu described in Joum. Ind. Chem. Soc. 1935, 306 by condensation of a correspondingly substituted B-amino crotonic acid ester of the general formula XV with a correspondingly substitutedmalon invention. Coupling being terminated, the 'dyestuff is isolated in the usual fashion, for instance, -by spraydrying. The monoazo dyes thus obtainable are'suited,

for example, for the dyeing and printing of cotton, wool and polyamides according toxall of the -convential dye- 7 ing and printing processes and yield yellow shades with good fastness properties, in particular a good fastness to light, perspiration and washing; The properties are I very good, particularly where in the compounds'of the 40 present invention Y equals to hydrogen. These dyes yi-' eld, when blended with turquoise dyestuffs, v'ery'valu- .able, brilliant, green shades. t v

i 5 According to the process of the present invention f I, flfl'these hydroxy-pyridonemonosulfonic acids contain common salt and may directly be used for the prepara- -'tiO.n of..dyestuffs.

t The following examples are given for thepurpose of illustrating the present invention. All temperatures are;

"given in degrees centigrade 'and'all'partsare par'tslby I lsoweightf I 7 EXAMPLE v t For the preparation of 4-methyl-6-hydroxy-2- pyridone-5-sulfonic acid, 350 parts chlorosulfonic acid are admixed at +20 -+30 with 15 parts common salt and. subsequently with 63 parts 4-methyl-6-hydroxy-2- pyridone. This mixture is stirred for 4 hours at +20 25, decomposed on 1000 parts of ice and stirred for 18 hours. Subsequently, the precipitated colorless 4- methyl6-hydroxy-2-pyridone-5sulfonic acid is sucked off, washed on the suction apparatus with 300 parts of a common salt solution of 24 Be and dried.

-Analysis: C H O NS: Calc.: N 6.8%; S 15.6%;

65 NS 1:2.29. Found: N =5.4%; S 12.5%; NS

The data of the analysis (NzS) show that a monosulfonation of the 4-methyl-6-hydroxy-2 pyridone has taken place, The fact that the values for the nitrogen and sulfur found are smaller than those calculatedis due to the common salt content of the product. The structure of the 4-methyl-6-hdyroxy-2-pyridone-5- sulfonic acid has been confirmed by the nuclear resonance spectrum.

10 The 3-cyano-4-methyl-6-hydroxy-2-pyridone can be obtained as indicated in'Example 1 in accordance with the method described by BOBBIT and SCOLA, loc. cit.

As intermediate product for the preparation of the 4-methyl-6-hydroxy-Z-pyridone required as initial comv EXAMPLE 3 Pchhd Serves Y y y y- For the preparation of the l.4-dimethyl-6-hydroxy-2-' pyridone which, as described y BOBBITT and pyridone-5-sulfonic acid 1 13 parts 1.4-dimethyl-6- SCOLA in Journ. Org. Chem. 25, 560, is obtainable by hd -2- id r introducted at +20 +25 condensation of ethyl aceto acetate with cyanaceta- 10 i 4 0 parts lf i id monohydrate S b mide in alcoholic alkali. lt is from this product that the ml at h same temperature, 90 parts bl f cyahc group in 'P is Split Off with Sulfuric acid 65% are allowed to run into this mixture and stirred for of 60% at 120C in accordance with the method 4 hours. The sulfonation batch is then decomposed on scribed by GIBSON and SlMONSEn in Journ. Chem. 1300 parts of ice. After stirring for 16 hours time at 1074 room temperature, the separated colorless 1.4-

' dimethyl-6-hydroxy-2-pyridone-5-sulfonic acid is EXAMPLE 2 sucked off, washed on the suction apparatus with 750 For the preparation of the 3-cyano-4-methyl-6- parts common salt solution of 24 Be and dried. hydroxy-Z-pyridone-S-su1fonic acid, 129 parts of the Analysis: C l-l O NS: Calc.: N 6.4%; S 14.6%; monosodium salt of the 3-cyano-4-methyl-6-hydroxy- N:S 1:2.25. Found: N 5.1%; S 11.7%; N:S 2-pyridone are introduced at +20 +25 into 450 122.29. parts sulfonic acid monohydrate. The mixture is stirred The data of the analysis (N:S) show that a monosulfor 1 hour, subsequently 300 parts oleum of 65% are fonation of the 1.4 -dimethyl-6-hydroxy-3-pyridone has added at the same temperature and stirring is contintaken place. Due to the common salt content of the ued for another 18 hours at +50". After cooling down 25 product the values for the nitrogen and sulfur found are to +20, the reaction batch is decomposed on 2000 smaller than those calculated. The structure of the 1.4- parts ice. Obtained is a limpid aqueous solution from dimethyl-6-hydroxy-2pyridone-5sulfonic acid has which the colorless 3-cyano-4-methyl-6-hydroxy-2- been confirmed by the nuclear resonance spectrum. pyridone-S-sulfonic acid being formed is separated by As intermediate product for the preparation of the the introduction of 400 parts common salt. The reacl.4-dimethyl 6-hydroxy-2-pyridone required as starting tion product is sucked off, washed on the suction appamaterial serves the l.4-dimethyl-3-cyano-6-hydroxy-2- ratus with 900 parts common salt solution of 24 Be pyridone which, as is analogously described by BOB- and dried. BITT and SCOLA, loc. cit., canbe prepared by con- Analysis: C H O N S: Calc.: N 12.2%; S 13.9%; densation of ethyl aceto acetate with an equimolecular N:S 1:].14. Found: N 8.4%; S 10.0%; N:S amount of N-methyl acetamide. The cleavage of the 1:1.17. cyano group in 3-position is effected as described in The data of the analysis (N:S) show that a monosul- Examaple 1. fonation of the 3-cyano-4-methyl-6-hydroxy-2- The following table illustrates further pyridone has taken place. Due to the common salt conhydroxy-pyridone-monosulfonic acids of the present tent of the product the values for the nitrogen and sul- 40 invention. In the case of initial pyridones of the general fur found are smaller than those calculated. formula V! which contain in one or more X-, Y- and/or The structure of the 3-cyano-4-methyl-6 hydroxy-2- Z-positioned substituents a hydroxyl group, not only a pyridone-SAsulfonic acid has been confirmed by the nusulfonation reaction takes place but also an esterificlear resonance spectrum. cation of the hydroxyl group(s). In the sulfonation. the The 3-positioned cyano group may be split off by sulfonic acid group is introduced into. the pyridone nuheating for several hours at 100 the 3-cyano-4-methylcleus. In the esterification, the OH-groups being pres- 6-hydroxy-2pyridone-5-sulfonic acid in an aqueous s0- ent in the X-, Y- and/or Z-positioned substituents are dium hydroxide solution of 33 Be. The reaction prodconverted to OSO H,groups.

. uct obtained is identical with the 4-methyl-6-hydroxy- The sulfonic acidester groups may be split off by 2-pyridone-5-sulfonic acid obtained according to EX- treating the reaction product with dilute acids or alkaample 1. lies.

Table and tautomeric forms thereof No. X Z formula calc; found N:S N:S

1 Cl-| -CH -H H C,H,,0 Ns l 2.29 12.31

/CH; 2 CH CH --H -H C H 0,NS l 2.28 1 2.32 -3 -(cH',) c|-i, H H C H O NS 1 2.28 112.31 4 (CH2)5--CH 3 H H CHHHO5NS l 2.29 l:2.32 5 -CH'CH2-CN -H H CBHBO'SNZS 121.14 l:l.18 6 -CH,CH,-OH H H C-,H,O. NS l'2.28 1:2.30 7 -CH2-OCH;, --H H C-,H90,NS l 2.28 1:2.3l

Table-Continued HOQS Y N HO and tautomenc forms I thereof 2 g No X Y Z formula calc.: found:

N:S N:S

78 ,-CH2CHZCN -CN -CH c fl o N s 110,77 110.75 79 CH -Cl-l OCl-l --CN CH;, C l-l O N s 1-1,14 1:1,[6

furthermore H038 -C,H O NS 1:228 1230 1-10 5 H C H 0 NS l:2.28 1:2.32

82 1-10 5 H c m o u s 111,14- l :l.l6-

CH 2CH2-NH2 EXAMPLE 4 The print may be fixed either by steaming at,

281 g. 4-,8-sulfatoethylsulfonyl-aniline are diazotized in the usual manner. The diazo suspension is added to a solution of 205 g. 6-hydroxy-4-methyl-2-pyridone-3- sulfonic acid in l000 c.c..aqueous 1N sodium hydroxide solution admixed with 120 g. sodium bicarbonate. The coupling being terminated, the pH is adjusted to 6.0 and the dyestuff ofthe'formula u 110 l o 50 g. of the above dyestuff 50 g. urea 5 425 g. hot water 450 g. alginatc thickener 15 g. sodium bicarbonate 10 g. sodium salt of the m-nitrobcnzcnc sulfonic acid 1000 g.

lO3-105 or by thermosetting. Subsequently, the fabric is rinsed and soaped-in both cases. 1 Weclaimz f, Q v 1. Hydroxy-pyrido e-monosulfonic acids of theformula and the tautomers thereof wherein X is alkyl having 1 to 6 carbon atoms; substituted alkyl wherein the alkyl moiety has from 1 to 6 carbon atoms and said substituent is selected from the group consisting of hydroxy and methoxy; cyclohexyl or substituted cyclohexyl wherein said cyclohexyl substituent is selected from the group consisting of chloro, methyl and methoxy.

The hydroxy'pyridonemonosulfoniC acids of 4. The hydroxy-pyridone-monosulfonic acids of claim *W X is alkyl 1 40211130" atoms claim 2 wherein Z is alkyl having 1 to 2 carbon atoms.

and Z hydrogen or alkyl having 1 to 4 fi f 5. The hydroxy-pyridone-monosulfonic acid of claim 3. The hydr0xy-pyridone-monosulfomc acids of 1 h i X is methyl and Z is hydrogen claim 2 wherein X is alkyl having 1 to 2 carbon atoms. 5 

1. HYDROXY-PYRODONE-MONOSULFONIC ACIDS OF THE FORMULA
 2. The hydroxy-pyridone-monosulfonic acids of claim 1 wherein X is alkyl having 1 to 4 carbon atoms and Z is hydrogen or alkyl having 1 to 4 carbon atoms.
 3. The hydroxy-pyridone-monosulfonic acids of claim 2 wherein X is alkyl having 1 to 2 carbon atoms.
 4. The hydroxy-pyridone-monosulfonic acids of claim 2 wherein Z is alkyl having 1 to 2 carbon atoms.
 5. The hydroxy-pyridone-monosulfonic acid of claim 1 wherein X is methyl and Z is hydrogen. 